吡啶氮或吡咯氮: 氮掺杂碳催化剂在电催化还原CO2中活性中心研究

doi:10.1016/S1872-2067(22)64122-6

催化学报 ›› 2022, Vol. 43 ›› Issue (9): 2405-2413.DOI: 10.1016/S1872-2067(22)64122-6

吡啶氮或吡咯氮: 氮掺杂碳催化剂在电催化还原CO₂中活性中心研究

商禹^a^,^†, 丁云轩^b^,^†, 张培立^a, 王梅^a, 贾玉飞^a, 徐云龙^a, 李亚晴^a, 范科^a^,^*(), 孙立成^a^,^b^,^c

^a大连理工大学化工学院, 精细化工国家重点实验室人工光合作用中心, 大连理工大学-瑞典皇家工学院分子器件联合研究中心, 辽宁大连116024, 中国
^b西湖大学理学院, 人工光合作用与太阳能燃料中心, 浙江杭州310024, 中国
^c瑞典皇家工学院化学学院, 斯德哥尔摩, 瑞典

收稿日期:2022-03-02 接受日期:2022-05-07 出版日期:2022-09-18 发布日期:2022-07-20
通讯作者: 范科
作者简介:第一联系人：
†共同第一作者.
基金资助:
国家自然科学基金(51772234);国家自然科学基金(22088102);国家自然科学基金(DUT19RC(3)063);中国辽宁省自然科学基金(2021-MS-126);中国辽宁省生物基化学品重点实验室

Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO₂ reduction

Yu Shang^a^,^†, Yunxuan Ding^b^,^†, Peili Zhang^a, Mei Wang^a, Yufei Jia^a, Yunlong Xu^a, Yaqing Li^a, Ke Fan^a^,^*(), Licheng Sun^a^,^b^,^c

^aState Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Centre on Molecular Devices, Institute for Energy Science and Technology, Dalian University of Technology, Dalian 116024, Liaoning, China
^bCenter of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, Hangzhou 310024, Zhejiang, China
^cDepartment of Chemistry, KTH Royal Institute of Technology, Stockholm 10044, Sweden

Received:2022-03-02 Accepted:2022-05-07 Online:2022-09-18 Published:2022-07-20
Contact: Ke Fan
About author:First author contact:
†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(51772234);National Natural Science Foundation of China(22088102);Fundamental Research Funds for the Central Universities(DUT19RC(3)063);Natural Science Foundation of Liaoning Province(2021-MS-126);Key Laboratory of Bio-based Chemicals of Liaoning Province of China

摘要/Abstract

摘要：

随着化石燃料的过度燃烧以及污染的持续加剧, 诸如海水酸化和气候变暖等问题逐渐显现, 因此人们开始日益关注大气中CO₂的浓度. 近些年, 由于碳基材料具有成本低、化学和机械稳定性良好、电导率高和有效抑制析氢反应等优点而被广泛用于CO₂还原反应(CO₂RR). 杂原子(B, P和N)掺杂可以有效地改变碳基材料电子结构并提高CO₂RR的选择性和活性. 其中, 由于氮原子具有独特的优势而被作为碳基材料的掺杂元素. 在无金属氮掺杂碳材料中, 吡啶氮被广泛地认为是催化活性中心, 而吡咯氮则被认为不具催化活性, 该观点仍存在争议.

本文首先通过密度泛函理论计算证明了吡咯氮的本征活性足以有效催化CO₂RR, 但由于与相邻吡啶氮位点的相互作用, 吡咯氮的活性被显著抑制. 此外, 进一步通过实验制备了不含吡啶氮的无金属氮掺杂碳球(NCS)作为CO₂RR电催化剂. NCS中的吡咯氮与CO₂RR的性能呈直接正相关, 表明其可以成为活性中心. 性能最佳的NCS可在CO₂RR中产生范围较宽的合成气(CO/H₂ (0.09‒12)), CO选择性最高可达71%. 在最优NCS中加入少量吡啶氮显著降低了CO₂RR的活性, 进一步验证了相邻吡啶氮位点对吡咯氮活性的抑制作用. 综上, 本工作揭示了各种氮物种之间的交互作用, 以及吡咯氮可以作CO₂RR活性位点的潜力; 进一步提高了我们对电催化作用机制的理解, 有助于高效电催化剂的设计和合成.

关键词: CO₂还原, 可调合成气, 碳球, 吡咯氮, 无金属催化剂

Abstract:

Pyridinic N is widely regarded as the active center while pyrrolic N has low-activity in metal-free N-doped carbon for electrocatalytic CO₂ reduction reaction (CO₂RR) to CO, but this viewpoint remains open to question. In this study, through density functional theoretical calculations, we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO₂RR, however, due to the interplay with the neighboring pyridinic N sites, the activity of pyrrolic N is dramatically suppressed. Then, experimentally, metal-free N-doped carbon spheres (NCS) electrocatalysts without significant pyridinic N content are prepared for CO₂RR. The pyrrolic N in NCS shows a direct-positive correlation with the performance for CO₂RR, representing the active center with high activity. The optimum NCS could produce syngas with a wide range of CO/H₂ ratio (0.09 to 12) in CO₂RR depending on the applied potential, meanwhile, the best selectivity of 71% for CO can be obtained. Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO₂RR, further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites. This work reveals the interaction between a variety of N species in N-doped carbon, and the potential of pyrrolic N as the new type of active site for electrocatalysts, which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high-efficient electrocatalysts.

Key words: CO₂ reduction reaction, Tunable syngas, Carbon sphere, Pyrrolic N, Metal-free catalysts

商禹, 丁云轩, 张培立, 王梅, 贾玉飞, 徐云龙, 李亚晴, 范科, 孙立成. 吡啶氮或吡咯氮: 氮掺杂碳催化剂在电催化还原CO₂中活性中心研究[J]. 催化学报, 2022, 43(9): 2405-2413.

Yu Shang, Yunxuan Ding, Peili Zhang, Mei Wang, Yufei Jia, Yunlong Xu, Yaqing Li, Ke Fan, Licheng Sun. Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO₂ reduction[J]. Chinese Journal of Catalysis, 2022, 43(9): 2405-2413.

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图/表 7

Scheme 1. Schematic procedure of the preparation for NCS-T and NCSP-T.

Fig. 1. (a) The models of CO2 adsorbed pyrrolic N, pyridinic N, graphitic N, double-site pyrrolic N (2pyr-N), double-site pyridinic N (2pyd-N), triple pyrrolic N (3pyr-N), triple pyridinic N (3pyd-N) and two pyridinic N sites induced nearby pyrrolic N (2pyd-pyr-N) in the theoretical calculations. (b) Free-energy landscape for CO2 reduction generating CO on different N sites. (c) Free energies between *COOH and *CO on different N sites.

Fig. 2. SEM image (a), size distribution (b), TEM image (c), HR-TEM image (d), TEM image (e) of NCS-70 and corresponding EDS mapping images of C, N and O of NCS-70. Raman spectra (f), XRD patterns (g) and FTIR spectra (h) of NCS.

Fig. 3. XPS spectra of C 1s (a), O 1s (b) and N 1s (c) of NCS-T (for clarity, XPS of NCS-50 and NCS-90 are shown in Supporting Information). Atomic content of carbon (d), oxygen (e) and oxygen species (f) in XPS spectra of NCS-T.

Fig. 4. Electrochemical performance of NCS-T. (a) LSV curves. (b) Faradic efficiency of CO (FECO). (c) Faradaic efficiency of H2 (FEH2). (d) Partial current densities for CO2 reduction to CO. (e) Partial current densities for HER. (f) Syngas ratio (CO/H2) dependent on the applied potential. (g) FE on the NCS-70 at different applied potentials. (h) Current density-time curve of NCS-70 at -1.25 V. The correlation between different species of N content and CO2RR performance to CO: pyrrolic N (i), graphitic N (j), and oxidized N (k).

Fig. 5. (a) LSV curves of NCSP-70 in 0.5 mol L?1 Ar and CO2-saturated KHCO3 solution. (b) LSV curves of NCSP-70 and NCS-70 in 0.5 mol L?1 CO2-saturated KHCO3 solution. (c) Partial current density of CO. (d) Partial current density of H2.

Fig. 6. (a) FE on the NCSP-70 at different applied potentials; (b) CO/H2 ratio produced by CO2RR catalyzed by NCSP-70 and NCS-70 dependent on the applied potential.

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吡啶氮或吡咯氮: 氮掺杂碳催化剂在电催化还原CO₂中活性中心研究

Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO₂ reduction

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